CN106117427A - A kind of preparation method of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer - Google Patents

A kind of preparation method of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer Download PDF

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CN106117427A
CN106117427A CN201610464323.5A CN201610464323A CN106117427A CN 106117427 A CN106117427 A CN 106117427A CN 201610464323 A CN201610464323 A CN 201610464323A CN 106117427 A CN106117427 A CN 106117427A
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fluorine
monomer
polymer
preparation
containing water
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CN106117427B (en
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陈文娟
张健
唐恩高
薛新生
朱玥珺
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China National Offshore Oil Corp CNOOC
CNOOC Research Institute Co Ltd
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CNOOC Research Institute Co Ltd
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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers

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Abstract

The invention discloses the preparation method of a kind of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer.The method comprises the steps: (1) under an inert atmosphere, and the cyclodextrin polymer of end group hydroxyl reacts with redox initiator, obtains reactant liquor 1;(2) be slowly added to acrylamide monomer in described reactant liquor 1 successively, fluorine-containing hydrophobic monomer, amphion choline function monomer carry out graft copolymerization;(3) in the reaction system of step (2), add sodium hydroxide to be hydrolyzed reaction, obtain described polymer;The structural formula of described fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer is as shown in formula I.The present invention fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymers synthesis technique is simply amplified, aqueous phase radical polymerization green non-pollution, the product of Series Molecules amount and structure can be obtained, and its thickening and shear resistant are significantly better than that conventional linear polyacrylamide polymer, there is field use prospect.

Description

A kind of preparation method of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer
Technical field
The present invention relates to the preparation method of a kind of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer, belong to high Molecular material field.
Background technology
Polymer displacement of reservoir oil tech is one of technical way of oil field development raising oil recovery factor, has good increasing Produce stable yields effect.The thickening property of polymer excellence can reduce water phase permeability and water-oil mobility ratio, expands sweep efficiency, reduces Residual oil saturation, thus improve oil recovery factor.
Partially hydrolyzed polyacrylamide (PHPA) base polymer or its modified product are the polymer displacement of reservoir oil being most widely used at present Agent.Although the extensive application of polymer, polymer spills the most cruelly in the defect of application process.Polymer is in preparation (stirring Device), conveying (pump, pipeline, valve), inject (sleeve pipe borehole) and during flowing through pore media by strong mechanical shear Cutting so that molecular chain rupture, molecular structure is destroyed, and molecular chain length reduces, thus causes polymer solution viscosity drastically Reducing, oil displacement efficiency declines.It is the Main Means improving polymer anti-shear performance that polymer carries out structure and composition modification.
Summary of the invention
It is an object of the invention to provide the preparation side of a kind of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer Method, the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer prepared by the present invention has higher viscosity and stronger Anti-shear performance.
The preparation method of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer provided by the present invention, including such as Lower step:
(1) under an inert atmosphere, the cyclodextrin polymer of end group hydroxyl reacts with redox initiator, is reacted Liquid 1;
(2) in described reactant liquor 1, acrylamide monomer, fluorine-containing hydrophobic monomer, amphion choline it are slowly added to successively Class function monomer carries out graft copolymerization;
(3) in the reaction system of step (2), add sodium hydroxide to be hydrolyzed reaction, obtain described polymer;
The structural formula of described fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer is as shown in formula I:
Wherein, core A is the cyclodextrin polymer of end group hydroxyl;
Arm B is by acrylic amide-acrylic sodium random copolymer segment, poly-fluorine-containing hydrophobic segment and poly-amphion choline The copolymer that function segment is in turn connected to form, and another termination of described acrylic amide-acrylic sodium random copolymer segment Branch is on described core A.
The viscosity-average molecular weight of described fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer can be 3,500,000~1000 Ten thousand, such as 10,000,000;
The degree of hydrolysis of described fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer can be 20%~40%, as 27%;
Described core A, described acrylic amide-acrylic sodium random copolymer segment, described poly-fluorine-containing hydrophobic segment and described The mass ratio of poly-amphion choline function segment can be 1:200~350:5~18:6~20, concretely 1:300:8.2~ 8.3:7.2~12.4,1:300:8.3:7.2 or 1:300:8.2:12.4.
Described poly-fluorine-containing hydrophobic segment is obtained by the polymerization of fluorine-containing hydrophobic monomer;
Described fluorine-containing hydrophobic monomer can be hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, methacrylic acid 13 In fluorine monooctyl ester, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate and trifluoroethyl methacrylate at least one;
Described poly-amphion choline function segment is obtained by the polymerization of amphion choline function monomer;
Described amphion choline function monomer can be for shown in methylacryloyl phosphocholine shown in formula II or formula III Methacryl yl carboxylic acid choline:
In formula III, n is the number between 1~3.
In above-mentioned preparation method, the cyclodextrin polymer of described end group hydroxyl is prepared according to the method comprised the steps:
In the basic conditions, cyclodextrin and epoxychloropropane carry out reacting and get final product;
Described cyclodextrin is beta-schardinger dextrin-.
In above-mentioned preparation method, described cyclodextrin can be 1:0.2~0.3 with the mass ratio of described epoxychloropropane, tool Body can be 1:0.24;
The temperature of described reaction can be 45~55 DEG C, and the time can be 5~8 hours, as reacted 6 hours at 50 DEG C;
Described alkalescence condition is transferred in row regulation and control by sodium hydrate aqueous solution, and the percent mass of described sodium hydrate aqueous solution contains Amount is 0.5~2%.
In above-mentioned preparation method, in step (1), described redox initiator be selected from following at least one: nitric acid Cerium ammonium, potassium peroxydisulfate, Ammonium persulfate., sodium peroxydisulfate and hydrogen peroxide;
Described redox initiator participates in reaction, in described aqueous solution, described oxidoreduction with the form of its aqueous solution The mass percent concentration of initiator can be 0.5%~3%, concretely 0.5%;
Described redox initiator can be 1.5~3:1 with the mass ratio of the cyclodextrin polymer of described end group hydroxyl, specifically Can be 2:1;
The temperature of described reaction can be 30~50 DEG C, and the time can be 30~60min, specifically can react under conditions of 40 DEG C 40min。
In above-mentioned preparation method, in step (2), described acrylamide monomer is with the form of acrylamide monomer aqueous solution Adding, the mass percent concentration of described acrylamide monomer aqueous solution can be 20~30%, concretely 25%;
Described fluorine-containing hydrophobic monomer adds with the form of emulsion, and described emulsion uses sodium lauryl sulphate and water to enter Row preparation, in described emulsion, the mass percent concentration of described fluorine-containing hydrophobic monomer can be 2~15%, concretely 5%;
Described amphion choline function monomer adds with the form of amphion choline function monomer aqueous solution, institute The mass concentration stating amphion choline function monomer aqueous solution can be 2~15%, concretely 5%.
In above-mentioned preparation method, the cyclodextrin polymer of described end group hydroxyl, described acrylamide monomer, described fluorine-containing dredge Aqueous monomer can be 1:220~420:9~25:7~23 with the mass ratio of described amphion choline function monomer successively, specifically Can be 1:320:18:15;
The temperature of described graft copolymerization can be 45~75 DEG C, and the time can be 5~10h, as anti-under conditions of 55 DEG C Answer 6h.
In above-mentioned preparation method, in step (3), the addition of described sodium hydroxide is the quality of acrylamide monomer 10%~20%, concretely 15%;
The temperature of described hydrolysis can be 90 DEG C~120 DEG C, and the time can be 1~3 hour, as little in carried out 3 at 120 DEG C Time.
Fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer prepared by the present invention can be as oil displacement agent for oil In the polymer displacement of reservoir oil of field, compound concentration scope can be 1200~3000mg/L, such as 1750mg/L.
The present invention has a following beneficial aspects:
The present invention fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymers synthesis technique is simply amplified, and aqueous phase is certainly It is polymerized green non-pollution by base, the product of Series Molecules amount and structure can be obtained, and its thickening and shear resistant are significantly better than that often Gage line polyacrylamide polymer, has field use prospect.
Accompanying drawing explanation
Fig. 1 is the thickening property figure of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer prepared by the present invention.
Fig. 2 is the anti-shear performance of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer prepared by the present invention Figure.
Detailed description of the invention
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.
HCD employed in following embodiment prepares as steps described below:
Add NaOH solution and the 15mL water of the 25wt% of 5.0g β-CD, 7.5mL, stir 1 hour, slowly drip 1.0mL epoxychloropropane (1.18g), after dropping, at a temperature of 50 DEG C, 6h, system 100mL third are reacted in stirring energetically Ketone precipitates, the white solid obtained, the water of crude product 100mL: it is unreacted that the mixed solution of ethanol=1:2 cleans removing repeatedly CD and expoxy propane class monomer, last white solid vacuum drying obtains product HCD.
Acryloyl group phosphorylcholine-monomer employed in following embodiment is the product of medicine company limited of Sigma of the U.S. Product, reagent abbreviation MPC, CAS accession number is 67881-98-5.
The product of the medicine company limited of Sigma of the acryloyl group carboxylic acid choline U.S. employed in following embodiment, reagent Abbreviation CBMA, CAS accession number is 24249-95-4, wherein n=1.
Dodecafluoroheptyl methacrylate employed in following embodiment is for avenging good fluorine chemistry of silicones Products, and reagent contracts Writing DFBMA, CAS registration number is 2261-99-6.
Embodiment 1, prepare fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer
By 25mg parent nucleus HCD, 95mL H2O is placed in there-necked flask, stirring and dissolving, is passed through nitrogen deoxygenation 45min, then Add ammonium ceric nitrate aqueous solution (50mg ammonium ceric nitrate is dissolved in 10mL water) under nitrogen protection, stirring reaction 30min at 40 DEG C, Acrylamide aqueous solution (8.0g acrylamide is dissolved in 24mL water), methacrylic acid 12 it is slowly added to successively in reactant liquor (450mg dodecafluoroheptyl methacrylate monomer is emulsifiable in 8.6mL water fluorine heptyl ester monomer emulsion, and emulsifying agent is dodecane Base sodium sulfonate 450mg), acryloyl group ethyoxyl phosphorylcholine-monomer aqueous solution (375mg acryloyl group ethyoxyl phosphocholine list Body is dissolved in 7.1mL water), then it is warmed up to 55 DEG C and reacts 6 hours, in reactant liquor, add 1.2g NaOH, water at 120 DEG C Solving 2 hours, dry, obtain 1# fluorine-containing water-soluble ultrabranching multiarm polymers, its viscosity-average molecular weight is about 10,000,000, degree of hydrolysis It is 27%.
In 1# fluorine-containing water-soluble ultrabranching multiarm polymers prepared by the present embodiment, HCD, acrylic amide-acrylic sodium without Rule copolymer segment, polymethylacrylic acid ten difluoro heptyl ester segment are 1 with the mass ratio of polypropylene acyl group phosphocholine segment: 300:8.3:7.2.
Embodiment 2, fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer
By 25mg parent nucleus HCD, 95mL H2O is placed in there-necked flask, stirring and dissolving, is passed through nitrogen deoxygenation 45min, then Add ammonium ceric nitrate aqueous solution (50mg ammonium ceric nitrate is dissolved in 10mL water) under nitrogen protection, stirring reaction 30min at 40 DEG C, Acrylamide aqueous solution (8.0g acrylamide is dissolved in 24mL water), methacrylic acid 12 it is slowly added to successively in reactant liquor (450mg dodecafluoroheptyl methacrylate monomer is emulsifiable in 8.6mL water fluorine heptyl ester monomer emulsion, and emulsifying agent is dodecane Base sodium sulfonate 450mg), (375mg acrylic acid carboxylic acid choline monomer is dissolved in 7.1mL water to acrylic acid carboxylic acid choline monomer solution In), then it is warmed up to 55 DEG C of reaction 6h, in reactant liquor, adds 1.2g NaOH, hydrolyze 2 hours at 120 DEG C, dry, to obtain final product 2# fluorine-containing water-soluble ultrabranching multiarm polymers, its viscosity-average molecular weight is about 10,000,000, and degree of hydrolysis is 27%.
In 2# fluorine-containing water-soluble ultrabranching multiarm polymers prepared by the present embodiment, HCD, acrylic amide-acrylic sodium without Rule copolymer segment, polymethylacrylic acid ten difluoro heptyl ester segment are 1:300 with the mass ratio of polyacrylic acid carboxylic acid choline segment: 8.2:12.4.
Embodiment 3, the performance test of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer
The performance of 1# and the 2# fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer preparing the present invention is carried out Evaluating, evaluation methodology and result are as follows, and wherein unaltered portion hydrolyzed polyacrylamide (i.e. " general polymer ") is industry Changing product, marque is FP6050, and purchased from SNF company of France, its structure is linear straight chain type.
(1) thickening property: take a certain amount of polymer, under 45 DEG C of water bath condition, prepares variable concentrations with deionized water Polymer solution, the relation of test polymer viscosity and concentration, evaluate the thickening property of polymer, result is as it is shown in figure 1, also Contrast with unaltered portion hydrolyzed polyacrylamide performance.
As shown in Figure 1, along with the increase of concentration, the viscosity of 1# Yu 2# fluorine-containing water-soluble ultrabranching multiarm polymers aqueous solution Dramatically increase, when concentration is 2000mg/L, 1# and 2# water-soluble ultrabranching aqueous polymer solution viscosity may be up to 113.6 and 129.3mPa s, far above the 65.8mPa s of unaltered portion hydrolyzed polyacrylamide.
(2) anti-shear performance: take the polymer solution that aimed concn is 1500mg/L, with the shearing of 1 grade of Rhein agitator 20s, measures its apparent viscosity before and after polymeric shear at different temperatures, calculates viscosity retention ratio, result as in figure 2 it is shown, And contrast with unaltered portion hydrolyzed polyacrylamide.
As shown in Figure 2, in concentrated water, 1# with 2# fluorine-containing water-soluble ultrabranching multiarm polymers solution is clipped After, viscosity retention ratio is maintained at about 58%, higher than about the 40% of unaltered portion hydrolyzed polyacrylamide.
(3) Oil Displacing Capacity: take the polymer solution that aimed concn is 1750mg/L, 20s sheared by one grade of Waring agitator The most standby.Use for laboratory artificial core, perm-plug method is respectively 500,2000 and 4000mD from top to bottom.With oil field, the Bohai Sea Compounding simulated oil with kerosene after comprehensive oil sample dehydration, 65 DEG C of viscosity are 70mPa s.First carry out water drive, aqueous when reaching more than 98% Turn polymer flooding.Polymer and water drive velocity are 3m/d, and polymer solution injected slurry volume is 0.3PV.Test result indicate that, 1# 11 can be improved than unaltered portion hydrolyzed polyacrylamide with the oil-recovering rate of 2# fluorinated water dissolubility dissaving polymer solution ~13%.
In sum, the fluorine-containing water-soluble ultrabranching multiarm polymers that the present invention provides is demonstrated by being better than unaltered portion water Solve the thickening of polyacrylamide, anti-salt, anti-shearing and Oil Displacing Capacity, can be applicable to polymer displacement of reservoir oil.

Claims (10)

  1. The preparation method of the most fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer, comprises the steps:
    (1) under an inert atmosphere, the cyclodextrin polymer of end group hydroxyl reacts with redox initiator, obtains reactant liquor 1;
    (2) in described reactant liquor 1, acrylamide monomer, fluorine-containing hydrophobic monomer, amphion choline merit it are slowly added to successively Graft copolymerization can be carried out by monomer;
    (3) in the reaction system of step (2), add sodium hydroxide to be hydrolyzed reaction, obtain described polymer;
    The structural formula of described fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer is as shown in formula I:
    Core A: ● arm B:
    Wherein, core A is the cyclodextrin polymer of end group hydroxyl;
    Arm B is by acrylic amide-acrylic sodium random copolymer segment, poly-fluorine-containing hydrophobic segment and poly-amphion choline function The copolymer that segment is in turn connected to form, and the other end of described acrylic amide-acrylic sodium random copolymer segment is grafted to On described core A.
  2. Preparation method the most according to claim 1, it is characterised in that: described fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide The viscosity-average molecular weight of amine polymer is 3,500,000~10,000,000;
    The degree of hydrolysis of described fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer is 20%~40%;
    Described core A, described acrylic amide-acrylic sodium random copolymer segment, described poly-fluorine-containing hydrophobic segment and described poly-two The mass ratio of property ion choline function segment is 1:200~350:5~18:6~20.
  3. Preparation method the most according to claim 1 and 2, it is characterised in that: described poly-fluorine-containing hydrophobic segment is by fluorine-containing hydrophobic Monomer polymerization obtains;
    Described fluorine-containing hydrophobic monomer be hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, methacrylic acid ten trifluoro monooctyl ester, In dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate and trifluoroethyl methacrylate at least one;
    Described poly-amphion choline function segment is obtained by the polymerization of amphion choline function monomer;
    Described amphion choline function monomer is methyl-prop shown in methylacryloyl phosphocholine shown in formula II or formula III Enoyl-carboxylic acid choline:
    In formula III, n is the number between 1~3.
  4. 4. according to the preparation method according to any one of claim 1-3, it is characterised in that: the polycyclic of described end group hydroxyl is stuck with paste Essence is prepared according to the method comprised the steps:
    In the basic conditions, cyclodextrin and epoxychloropropane carry out reacting and get final product;
    Described cyclodextrin is beta-schardinger dextrin-.
  5. Preparation method the most according to claim 4, it is characterised in that: described cyclodextrin and the quality of described epoxychloropropane Ratio is 1:0.2~0.3;
    The temperature of described reaction is 45~55 DEG C, and the time is 5~8 hours.
  6. 6. according to the preparation method according to any one of claim 1-5, it is characterised in that: in step (1), described oxidoreduction Initiator selected from following at least one: ammonium ceric nitrate, potassium peroxydisulfate, Ammonium persulfate., sodium peroxydisulfate and hydrogen peroxide.
  7. 7. according to the preparation method according to any one of claim 1-6, it is characterised in that: in step (1), described oxidoreduction Initiator participates in reaction with the form of its aqueous solution, and in described aqueous solution, the mass percent of described redox initiator is dense Degree is 0.5%~3%;
    Described redox initiator is 1.5~3:1 with the mass ratio of the cyclodextrin polymer of described end group hydroxyl;
    The temperature of described reaction is 30~50 DEG C, and the time is 30~60min.
  8. 8. according to the preparation method according to any one of claim 1-7, it is characterised in that: in step (2), described acrylamide Monomer adds with the form of acrylamide monomer aqueous solution, and the mass percent concentration of described acrylamide monomer aqueous solution is 20 ~30%;
    Described fluorine-containing hydrophobic monomer adds with the form of emulsion, and described emulsion uses sodium lauryl sulphate and water to join System, in described emulsion, the mass percent concentration of described fluorine-containing hydrophobic monomer is 2~15%;
    Described amphion choline function monomer adds with the form of amphion choline function monomer aqueous solution, and described two The mass concentration of property ion choline function monomer aqueous solution can be 2~15%.
  9. 9. according to the preparation method according to any one of claim 1-8, it is characterised in that: the polycyclic of described end group hydroxyl is stuck with paste The mass ratio of acrylamide monomer smart, described, described fluorine-containing hydrophobic monomer and described amphion choline function monomer is successively For 1:220~420:9~25:7~23;
    The temperature of described graft copolymerization is 45~75 DEG C, and the time is 5~10h.
  10. 10. according to the preparation method according to any one of claim 1-9, it is characterised in that: in step (3), described hydroxide The addition of sodium is the 10%~20% of the quality of acrylamide monomer;
    The temperature of described hydrolysis is 90 DEG C~120 DEG C, and the time is 1~3 hour.
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CN104844760A (en) * 2015-05-18 2015-08-19 中国海洋石油总公司 Water-soluble hyper-branched polymer oil displacement agent and preparation method thereof
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